Materials and methods for the separation of copper ions and ferric iron in liquid solutions

ABSTRACT

A silica-polyamine based extraction material removes selected transition metal ions from solution in the presence of iron ions. The silica-polyamine base is a reaction product of a polyamine and a covalently anchored trifunctional hydrocarbylsilyl that yields non-crosslinked amino groups to which pyridine function group is attached. The extraction material is particularly useful in selectively removing copper from low concentration, low pH leach solutions separating copper from ferric iron or chloride ions. The product is a durable, high capacity extraction material that selectively captures copper at high flow rates and releases that copper into highly concentrated solutions.

[0001] The subject invention was made with government support under aresearch project supported by the National Science Foundation Grant No.9961006. The government has certain rights in this invention.

BACKGROUND OF THE INVENTION

[0002] In recent years, hydrometallurgical processes for the extractionof copper from ore have supplanted traditional pyrometallurgicalmethods. Pyrometallurgical methods involve the use of fire to extractpure metals from ore by smelting. Increased awareness of theenvironmental impact of these processes however have lead to an increasein environmental standards and the concomitant increase in the capitalcost and operating cost of smelter equipment. Hydrometallurgicaltechniques have thus become a preferred method for the extraction ofcopper from copper ores.

[0003] Hydrometallurgical techniques involve the extraction or leachingof copper from copper ores into aqueous leach solutions. Ore is treatedwith aqueous solutions which dissolve the copper from the ore. Purecopper is then recovered from the leach solutions by solvent extractionand then electrowinning. Electrowinning is a process in which copper isplated onto an electrode from an aqueous solution containing highconcentrations of isolated copper ions.

[0004] An efficient leaching system uses dilute solutions of sulfuricacid to extract copper from copper oxide and oxide/sulfide containingores. Ferric (iron(III)) ions are often added to the acid solutions toimprove the efficiency of the leaching process by oxidizing the copper(I) to its more soluble copper (II) form and sulfide to sulfur. Theresulting leach solutions contain not only soluble copper and sulfate atlow pH but they also contain a variety of metals including iron,manganese, aluminum, magnesium and molybdenum of which highconcentrations of iron is the primary concern. Another efficientleaching system is chloride leaching. Chloride leaching is particularlyeffective at leaching copper from sulfide containing copper ores such aschalcopyrite. In this process ferric chloride is used as the source ofchloride ions to complex the copper and to oxidize the copper (I) tocopper (II) contributing to a high iron concentration in the leachsolution.

[0005] The copper concentrations in the leach solutions can range fromabout, 1 gram/liter (g/L) to about 50 g/L with typical concentrationsfalling between 1 g/L and 6 g/L. The pH of these solutions rangesbetween 1.2 and 2.2 pH units. Copper concentrations in a typicalelectrowinning tank however are between about 30 g/L and 35 g/L. It istherefore necessary to extract and concentrate the copper in these mixedacid leaches before purifying the copper by electrowinning.

[0006] The technology most widely used to extract and concentrate thecopper in these mixed acid leach solutions is solvent extraction. In thesolvent extraction process water soluble heavy metal salts are complexedwith organic ligands to produce low polarity or neutral charge complexesthat have limited solubility in water but are highly soluble in anorganic solvent (organic phase) which is immiscible with water. Ligandssuch as aryl-hydroxyoximes are used for this purpose. These ligandsselectively bind to the copper ions in the mixed metal solutions tocreate a charge neutral copper complex. These complexes are soluble inan organic solvent. Inthis way copper is selectively transferred intothe organic phase. Salts can also be added to the aqueous phase to forcethe metal complexes into the organic phase. Other variations of thisprocess incorporate ligands which form micelles in the aqueous phase orligands which stay in the organic phase and are polar on one end and soare drawn to the aqueous-organic interface where they react with themetals to form non-polar organic soluble complexes soluble in theorganic phase. When the organic phase becomes saturated with relativelyhigh concentration of complexed copper, the copper must be decomplexedand released into the clean aqueous phase for final electrowinning. Someof the problems associated with the solvent extraction process includethe necessity to execute multiple wash steps of the organic phase whenchloride leach solutions are being treated; the need to add equilibriummodifiers to facilitate the uptake into and release of copper fromorganic phase and the formation of “crud” that forms at theaqueous-organic phase interface causing equipment fouling. Organicsolvent and ligand loss further complicates the process. The primarydrawback with this technology however is the organic phase. The solventsused in the organic phase include benzene, toluene, chloroform, hexanesand octanes among others. Kerosene is the solvent of choice for mostlarge scale production mining operations. These solvents are typicallytoxic, flammable, and have adverse environmental inpacts. Solvent lossduring the extraction process extracts a negative economic toll. Ligandand equilibrium modifier loss is also an environmental and economicproblem associated with the solvent extraction process.

[0007] An alternative to the solvent extraction processing ofhydrometallurgical solutions is the use of swellable resin beads as anextraction medium. Swellable resin beads have a long history as thematrix on which ion exchange and metal ion chelation technologies arebuilt. These swellable resin beads are generally lightly crosslinkedpolystyrene which is modified to accommodate the addition of pendant ionexchange or chelating ligands and occasionally other groups to decreasethe hydrophobicity of the polymer. Copper selective ligands have beenchemically bonded to polystyrene beads for the processing of copperleaches. There are however problems associated with using swellableresin bead technology in high throughput operations. Lightly crosslinkedpolystyrenebeads are highly porous and the extractant ligands are boundthroughout the polymer matrix. Many, if not most, of the ligands areburied deep within the polymer bead. The feed solution must diffusethrough the bead to reach these sites for extraction to take place. Therequired process flow rates are often much faster than the rate ofdiffusion through the resin bead. For this reason a material that mayhave a high capacity in a batch application where the extractant and thefeed solution have long contact times has greatly reduced capacity inflow applications. Because of the porous nature of the resin beads theyalso have a tendency to collapse when subjected to the pressuresgenerated by the fast moving solution in a column application. The beadsat the exit end of the column flatten and pack more tightly togetherwhich in turn causes an increase in the backpressure of the system. Thiscauses a decrease in metal ion capacity and necessitates periodicbackwashing of the column thereby limiting the useful lifetime of thematerial. In addition, chloride is often present in the leach solutionand will contaminate the strip solution. This contamination is notcompatible with electrowinning. This is a problem with both the solventextraction process and currently employed resin technologies.

[0008] From the foregoing it is apparent that the technical challengeposed in the recovery of high grade copper from low grade ore is todevise an efficient, environmentally safe method of selectivelyextracting copper from low concentration, low pH leach solutions toproduce high concentration, high purity aqueous solutions suitable forelectrowinning (i.e. free of ferric and chloride ions).

SUMMARY OF THE INVENTION

[0009] The invention is a matrix-polyamine based material that extractsand separates selected transition metal ions from iron (III) ions from asolution containing a mixture of metal ions. In a preferred embodiment,the subject extraction material selectively extracts copper (II) fromlow pH solutions in the presence of iron (III) ions. Thematrix-polyamine based material is rigid and durable in order towithstand high throughput conditions and requires the use of no organicsolvents in its use and only a few in its manufacture. In a particularlypreferred embodiment, the matrix is silica gel which is washed with acidto maximize surface hydroxyl groups. The gel is then dried and partiallyrehydrated. The hydrated surface of the silica gel is reacted with ashort chain trifunctional silane having hydrocarbon substituentscontaining 1-6 carbon atoms, trifunctional leaving groups on the siliconatom that provide sites for covalently bonding the hydrocarbylsilyl tothe silica gel surface through Si—O bonds, and a terminal leaving groupthat provides a site for covalently bonding a polyamine to thehydrocarbylsilyl through carbon-nitrogen bonds. A polyamine is thenreacted with the hydrocarbylsilyl formed from the silanization of thehydrated gel surface to form an aminohydrocarbyl polymer covalentlybound to the silica gel surface. The silica-polyamine is then reactedwith picolylchloride (2-chloromethyl pyridine) or with pyridine2-carboxaldehyde to create a highly selective extraction material.

[0010] A three step high throughput system using the silica-polyamineextraction material of the subject invention is also described. Thefirst step of the process selectively extracts copper from leachsolutions containing high concentrations of ferric ions with no addedsolution modifiers. The second step purges the extracted copper ofchloride ions using a saturated solution of sodium sulfate or a dilutesulfuric acid solution. Thirdly, the copper is stripped from theextraction material with sulfuric acid to yield a concentrated coppersolution suitable for electrowinning. The column is ready to be reloadedafter rinsing with water.

BRIEF DESCRIPTION OF THE FIGURES

[0011]FIG. 1 shows the concentration of copper (II) and iron (III)remaining in the simulated mine leachate solution after being pumpedthrough a column of silica-polyvinylamine/picolyl gel. □ Fe(III), ▪Cu(II)

[0012]FIG. 2 shows the concentration of copper (II) and iron (III) inthe strip solution of the column used in FIG. 1. □ Fe(III), ▪ Cu(II)

[0013]FIG. 3 shows the molar fraction of metal ions adsorbed fromsolution by the extraction material of the subject invention against theoriginal metal ion concentration of that solution compared with apolystyrene resin produced by Dow Chemical (XFS 43084).  XFS Cu, ◯ XFSFe, ▪ 250-500 μmD2P-PVACu, □ 250-500 μmD2P-PVAFe, ♦ 90-105 μm D2P-PVACu, ⋄ 90-105 μm D2P-PVA Fe

[0014]FIG. 4 shows the adsorptive profiles of the copper selectiveextraction material of the subject invention compared with Dow Chemical(XFS 43084) over a range of pHs. ♦ 90-105 μmD2P-PVA Cu, ⋄ 90-150 μmS2P-PVAFe, ▪ 250-500 μm D2P-PVA Cu, □ 250-500 μm D2P-PVA Fe,  XFS Cu, ◯XFS Fe

[0015]FIG. 5 shows copper (II) and iron (III) capacity (mmol/g) over anextended period of use in a column-type system. Capacities were testedat a flow rate of 2 bed volumes/min. ♦ D2P-PVA Cu, ⋄ D2P-PVA-Fe,  XFSCu, ◯ XFS Fe

DETAILED DESCRIPTION OF THE INVENTION

[0016] The invention is a matrix-polyamine based material for theextraction of selected transition metals from iron (III) ions. In aparticularly preferred embodiment, the matrix-polyamine based extractionmaterial selectively extracts copper (II) ions from acidic solutions inthe presence of iron (III) ions. Picolylchloride or pyridine2-carboxaldehyde attached to a silica-polyamine base provides anextraction material that is highly selective for these copper ions.

[0017] The matrix-polyamine base is known and has been described in U.S.Pat. Nos. 5,695,882 and 5,997,748. These patents are herein incorporatedby reference. The surface of the matrix is chemically treated so as tocovalently bind the reaction product of a polyamine with ahydrocarbylsilyl, such as the preferred haloalkylsilyl, to the matrixsurface. This can be accomplished, for example, by first reacting ashort chain trifunctional silane having a hydrocarbon substituentcontaining 1-6 carbon atoms and a terminal leaving group, such as ahaloalkyl trifunctional silane, with the surface of the matrix in amanner such that the hydrocarbylsilyl is covalently bound with thematrix surface and then reacting a polyamine, such as polyethyleneimine,with the hydrocarbylsilyl to bind the polyamine to the hydrocarbylsilyl.The step of reacting the polyamine with the hydrocarbylsilyl must besuch that it will yield multisite bound, but non-crosslinked, aminogroups.

[0018] Briefly, the matrix-polyamine base material is prepared byboiling the matrix in acid, drying and partially rehydrating the matrixsurface. In the exemplified embodiment, the matrix is silica gel. Thesilica gel surface can be hydrated by applying a moisturized atmosphere,such as air passed through a saturated aqueous sodium bromide solution,to the surface in a controlled environment until a predeterminedhumidification has been attained as determined by the mass increase.

[0019] The hydrated gel surface is then contacted with the above-definedshort chain trifunctional silane, such as a haloalkyl trifunctionalsilane, in the presence of an inert organic solvent. The reactionbetween the hydrated surface of the silica gel and the silane produces ahydrocarbylsily that is covalently bonded to the gel surface bysiloxanyl (Si—O) groups. After the reaction between the hydrated surfaceand the silane, the silanized gel is rinsed with an inert organicsolvent and dried.

[0020] The silanized and dried gel surface is then contacted withpolyamine in the presence of an inert organic solvent or water toproduce a multisite bound non-crosslinked polyamine coating on thematrix surface.

[0021] Suitable trifunctional groups on the silica of the silanizingagent include trichloro, trimethoxy, and triethoxy groups; trichlorobeing preferred. Suitable groups for the silanizing agent on thehydrocarbyl fragment include bromine, chlorine and iodine, tosylate,mesylate, brosylate, and triflate; bromine and chlorine being preferred.Suitable hydrocarbyl groups include short chain aliphatic hydrocarbonshaving 1-6 carbon atoms; propyl being preferred, based on pricing of thetrichlorosilyl halide. A preferred molecular weight (M.W.) range for thepolyamine is 300-60,000; with polyvinylamine or polyalylamine in thatrange being most preferred.

[0022] Any number of suitable support materials may be substituted inplace of the silica gel for use as an extraction material; silica gelmerely being preferred because of its availability in sizes particularlysuitable for use in continuous-flow extraction processes.

[0023] A particularly preferred matrix-polyamine base material comprisesan alkylated silica gel where the silica gel surface is first reactedwith a haloalkyltrichlorosilane and, then that reaction product isfurther reacted with polyvinylamine to yield a polyvinylaminoalkylsilylactivated surface.

[0024] The sequence of formulating the matrix-polyamine base materialhas some critical components. First, the matrix surface is washed withan acid, for example, nitric acid, dried and rehydrated to insure that amonolayer of water overlays the surface. Second, the clean and hydratedsurface must be silanized before the polyamine is brought into thereaction. Polyamine addition is commenced only after the silanizationprocedure has been completed. By silanizing the hydrated surface with asilane having a short chain hydrocarbyl substituent containing 1-6carbon atoms and a terminal leaving group, the surface to the matrixmaterial will be virtually completely covered by Srf-O—Si-hydrocarbylgroups, where Srf represents the matrix surface, and by lateral Si—O—Sibonds. Hydration of the surface promotes the formation of these lateralbonds. The result is a horizontally polymerized matrix surface,covalently bound to the surface by Si—O bonds and cross-linked bySi—O—Si bonds with essentially few or no —OH groups left unreacted onthe matrix's surface. The short hydrocarbyl chains extend from thelaterally polymerized silyl groups and not from the matrix surface, andare not themselves cross-linked. As a consequence, of this form ofsilanization, the hydrocarbylated matrix surface becomes hydrolyticallystable in both high and low pH solutions. Polyamine addition to thecross-linked, silanized surface anchors, results in the substitution ofamino groups onto the ends of short hydrocarbyl chains withoutdestabilizing either the matrix surface or the covalent bonds with thehydrocarbyl substituent. In the context of a preferred process,employing a short chain trifunctional alkyl silane containing 1-6 carbonatoms, the result is a densely alkylated extraction material surface,that is optimal for bonding amino groups and for addition offunctionalizing groups or ligands.

[0025] Selectivity for certain transition metal ions in the presence offerric iron is achieved by the addition of a pyridine functional groupto the matrix-polyamine base material. These pyridine functional groupscan be a pyridine ring containing an alkyl chain with 1-4 carbons with aterminal halogen tosylate, mesylate, brosylate and triflate or apyridine ring containing an alkyl chain with 1-4 carbons with a terminalaldehyde. Synthesis of matrix-polyamine/amino or imino pyridineextraction material is accomplished in two ways. The first way (MethodA) converts the pyridine nitrogen of the picolylchloride hydrochloridesalt from the acid form to the free base form using a strong base. In apreferred embodiment, potassium hydroxide is used as the base. The freebase pyridine moiety of picolylchloride is then separated from theresulting salt before adding it to the matrix-polyamine base. In thesecond step the solution containing the free base pyridine moiety isadded to the matrix-polyamine/methanol slurry. In a second embodimenttriethylamine is used as the base. The triethylamine, the pyridinecontaining ligand and the matrix-polyamine material are all combined ina single reaction. In this embodiment the base is used to convert thepyridine containing ligand to the free base form and scavenge the acidformed during the reaction. The resulting 2-picolylamine polyamine isshown in Formula 1. The second way (Method B) involves the addition ofpyridine 2-carboxaldehyde directly to silica-polyamine. A slurry of thesilica polyamine and an organic solvent is heated for several hours at60-90° C. Method B yields 2-pyrindine carboximine polyamine shown inFormula 2.

[0026] Properties afforded the extraction material of the subjectinvention through this synthetic route include long material lifetime,high capacities for many heavy metal ions, selectivity for heavy metalions with no interference from alkali or alkaline earth metals, theability to extract these metal ions at high flow rates to very lowlevels, the ability to release these captured metals in highlyconcentrated solutions and most importantly selectivity for copper ionsin the presence of other transition metals ions including ferric ions.

[0027] The advantageous properties of the subject material are revealedby performance defining tests. These tests can be divided into two broadcategories, batch tests and flow tests. Batch tests are conducted bsubjecting a predetermined amount of extraction material to apredetermined amount of feed solution for a set amount of time. Batchtests are used to determine capture kinetics, absorption isotherms, andpH profiles. Flow tests are conducted by flowing the feed solutionthrough the extractant. Flow tests elucidate how the materials willperform under process conditions.

[0028] The gel containing the picolyl group was tested under flowconditions to determine its ability to separate copper from ferric iron.The feed solution, a simulated or leach solution, contained a 1:3 weightratio of copper (II) to iron (III). The copper was added as copper (II)sulfate and the iron as iron (III) chloride, this formulation produced achloride ion element in the solution as well as the heavy metals tofurther simulate leach solutions. The solution was used at its intrinsicpH of ˜1.2. The feed solution was applied to a column containingsilica-polyvinylamine/picolyl gel. The feed solution was allowed to flowthrough the column. A strip solution of sulfuric acid was used torelease metal captured and held on the gel surface. The results of thesepreliminary flow tests revealed that the strip solution contained aratio of approximately 100:1 copper to iron.

[0029] Early trials however revealed a significant chloride ionconcentration in the strip solution. The gel has a very high bindingaffinity for copper, for the material made by Method A concentratedsulfuric acid or 4N acid heated to 70° C. is required to completelystrip the copper from the gel. The material made by Method B can bestripped with 4N acid. A second series of trials was carried out withthe objective of reducing the chloride ion content of the eluant orstrip solution. To accomplish this saturated sodium sulfate solution waspumped through the column after it was loaded with copper from thesimulated leach solution. The gel was then stripped with concentratedsulfuric acid and the strip solution was analyzed. The chloride ioncontent in the strip solution was below detection using ionchromatography. The sodium sulfate solution was analyzed for copper andwas found to contain only low concentrations of the metal, for example,23 ppm.

[0030] The matrix-polyamine/picolyl extraction material of the subjectinvention provides a basis on which to build an environmentallyfriendly, efficient system, to extract copper from acidic low copperconcentration leach solutions and produce a highly concentrated highpurity copper solution suitable for electrowinning. A three step highthroughput system provides high purity copper from low concentrationleach solutions. The first step of the process selectively extractscopper from leach solutions containing high concentrations of ferricions with no added solution modifiers. The second step purges theextracted copper of chloride ions using a saturated solution of sodiumsulfate or dilute sulfuric acid solution. Thirdly, the copper isstripped from the extraction material with sulfuric acid to yield aconcentrated copper solution suitable for electrowinning. The column isready to be reloaded after rinsing with water.

[0031] The economic benefits realized from this process are eliminationof cost associated with solvent and ligand loss, predicted decreasedenergy consumption and predicted decreased processing time relative tothe solvent extraction systems currently in use. Major environmentalbenefits are realized with the elimination of organic solvents from theprocess. Major economic advantages over currently available chelatorresins are lower material cost and longer usable lifetimes.

[0032] Although the above discussion and the following examples focusupon a preferred embodiment of the extraction material of the subjectinvention, it is noted that the subject invention can be used toseparate other transition metal ions from iron (III) ions. For example,ions, including but not limited to, cobalt (II), nickel (II) and zinc(II) can be selectively extracted in the presence of iron (III) ionsusing the extraction material of the subject invention.

[0033] The following examples are offered to further illustrate but notlimit both the composition and the methods of the present invention. Allpercentages are by weight and all solvent mixture proportions are byvolume unless otherwise noted.

EXAMPLE 1

[0034] Preparation of silica-polyvinylamine/2-picolylchloride (D2P-PVA)(Method A)

[0035] 1. Amorphous silica gel (such as Crosfield, 90-105 microns (μm),150 Å pore size with 375 meters²/grams (g) surface area) (200 g) wasmixed with 1N nitric acid (800 milliliters (mL)) in a 2 liter (L)three-necked round bottom flask. The contents were degassed for twominutes (min). After degassing, the flask was put into a heating welland a reflux condenser, a thermometer and a mechanical stirrer wereattached to the flask. The contents of the flask were stirred and heatedat 100° F. for 6 hours (hr). At the end of the 6 hr heating, thecontents were cooled to room temperature and dumped into a 3 L sinteredglass funnel. The gel was washed three times, 800 mL each, withdeionized (DI) water. The gel was further washed with methanol threetimes (800 mL each). After most of the methanol was removed, the gel wasspread in an open pan and air dried over night. The air-dried gel in thepan was placed in an oven and dried at 120° F. for 2-4 hr until constantweight was reached. Typical weight lost during this acid wash is about6.4-7.1%.

[0036] 2. The oven-dried gel (200 g) was placed in a 3 L sintered glassfunnel. Moisturized air from a saturated solution of sodium bromide waspassed through the gel from the outlet of the funnel. The flow rate ofthe moisturized air was regulated so that a fountain-like motion of thegel was observed. During this step, the weight of gel was checked everytwo hr until constant weight was obtained. Typical time required isabout 12-16 hr and the average weight gain is 4.2-4.6%.

[0037] 3. The hydrated gel (200 g) was then placed in a 2 Lsingle-necked round bottomed flask. Heptane (704.9 mL, dried overmolecular sieves) and bromopropyltrichloro silane (951 mL, freshlydistilled) were well mixed in a 1 L Erlenmeyer flask and slowly pouredinto the round bottom flask via a funnel. Hydrochloric gas formedvigorously and the contents were gently swirled to let more hydrochloricgas evolve. After most of the gas evolution subsided, the flask wasattached to a mechanical vacuum pump and degassed for 5 min. At the endof the 5 min, the flask was attached to a mechanical motor and spunslowly for 16 hr. After 16 hr of spinning, the contents were poured intoa 3 L sintered glass funnel and the gel was washed successively withheptane, three times, methanol, three times, water, three times, andfinally methanol, three times, (800 mL each). The gel was air dried inan open pan and then in the oven at 110° C. for 2 hr. Typical weightgain is about 16-30%.

[0038] 4. Free base poly(vinyl amine) (PVA) (M.W. 5,000) (pH=13) in a20.8% solution (400.00 g), and methanol (400 mL) were mixed in a 3 Lround bottom flask. The bromopropyl gel (200.00 g) from step 3 was addedto the flask. The flask was swirled to wet all of the bromopropyl geland to form a slurry. The contents were degassed using an aspiratoruntil the foaming stopped. After the degassing process the flask wasattached to a motor and spun for a period of between 2 hr and 3 days atroom temperature. At the end of the stirring process the contents waspoured into a 3 L sintered glass funnel and washed with DI water threetimes, washed once with 4N sulfuric acid, three times with DI water,once with 4N ammonium hydroxide, three times with DI water and threetimes with methanol. The resulting PVA gel was air dried in an open pan.Typical weight gains are between 12 and 18 percent.

[0039] 5. 2-picolylchloride hydrochloride (24.61 g) was dissolved inmethanol (60 mL) in a 150 mL beaker. Powdered potassium hydroxide wasdissolved in the 2-picolylchloride hydrochloride solution. The resultingprecipitate was filtered using a Buchner funnel with filter paper. Thefiltrate was collected and transferred to a 500 mL 3-neck round bottomflask. Sixty mL of tetrahydrofurran (TBF) was added to the solution inthe round bottom flask and swirled until it was well-mixed. Theair-dried PVA gel (30.00 g) from the previous step was added to theflask. The flask was swirled to wet all of the PVA gel and form aslurry. The contents were degassed using an aspirator until the foamingstopped. After degassing, the flask was put into a heating well. ATEFLON paddle glass rod mechanical stirrer was fitted into the centerneck. The pH was checked and adjusted to between 9-13 pH units,preferably 13, by manually adding, dropwise, 2N potassium hydroxide inmethanol. While stirring the contents were heated to reflux. The pH waschecked every hour and manually adjusted with 2 N potassium hydroxide inmethanol as needed to maintain a pH of 9-13 while refluxing. After 9 hrof refluxing the contents were cooled to room temperature and pouredinto a 500 mL sintered glass funnel and washed with 120 mL each ofmethanol, three times, DI water, three times, concentrated sulfuricacid, once, DI water, three times, and methanol, three times. Theresulting gel (D2P-PVA) was air dried in an open pan.

EXAMPLE 2

[0040] Preparation of silica-polyethyleneimine/2-picolylchloride(D2P-PEI)(Method B)

[0041] 1. Complete steps 1-3 of Example 1.

[0042]2. Free base poly(ethyleneimine) (PEI) (M.W. 1,200) (pH=13) in a50 % solution (300.00 g), distilled water (100 mnL) and methanol (300mL) were mixed in a 3 L round bottom flask. The bromopropyl gel (200.00g) from step 3 was added to the flask. The flask was swirled to wet allof the bromopropyl gel and to form a slurry. The contents were degassedusing an aspirator until the foaming stopped. After the degassingprocess the flask was attached to a motor and spun for a period ofbetween 2 hr and 3 days at room temperature. At the end of the stirringprocess the contents was poured into a 3 L sintered glass funnel andwashed with DI water three times, washed once with 4N sulfuric acid,three times with DI water, once with 4N ammonium hydroxide, three timeswith DI water and three times with methanol. The resulting PEI gel wasair dried in an open pan. Typical weight gains are between 12 and 18percent.

[0043] 3. 2-picolylchloride hydrochloride (24.61 g) was dissolved inmethanol (60 mL) in a 150 mnL beaker. Powdered potassium hydroxide wasdissolved in the 2-picolylchloride hydrochloride solution. The resultingprecipitate was filtered using a Buchner funnel with filter paper. Thefiltrate was collected and transferred to a 500 mL 3-neck round bottomflask. Sixty mL of tetrahydrofurran (THF) was added to the solution inthe round bottom flask and swirled until it was well-mixed. Theair-dried PEI gel (30.00 g) from the previous step was added to theflask. The flask was swirled to wet all of the PEI gel and form aslurry. The contents were degassed using an aspirator until the foamingstopped. After degassing, the flask was put into a heating well. ATEFLON paddle glass rod mechanical stirrer was fitted into the centerneck. The pH was checked and adjusted to between 9-13 pH units,preferably 13, by manually adding, dropwise, 2N potassium hydroxide inmethanol. While stirring the contents were heated to reflux. The pH waschecked every hr and manually adjusted with 2 N potassium hydroxide inmethanol as needed to maintain a pH of 9-13 while refluxing. After 9 hrof refluxing the contents were cooled to room temperature and pouredinto a 500 mL sintered glass funnel and washed with 120 mL each ofmethanol, three times, DI water, three times, concentrated sulfuricacid, once, DI water, three times, and methanol, three times. Theresulting gel (D2P-PEI) was air dried in an open pan. Typical weightgains are between 10 and 35%.

Example 3

[0044] Preparation of silica-polyallylamine/2-picolylchloride(D2P-PAA)(Method C)

[0045] 1. Complete steps 1 and 2 of Example 1.

[0046] 2. The hydrated gel (100 g) was then placed in a 1 Lsingle-necked round bottomed flask. Heptane (˜353 mL, dried overmolecular sieves) was added to chloropropyltrichloro silane (47 mL) in a500 mL graduated cylinder to bring the total solution volume up to 400mL . The graduated cylinder was agitated frequently to ensure mixing ofthe reagents. The contents of the graduated cylinder were slowly pouredinto the round bottomed flask via a funnel. Hydrogen chloride gas formedvigorously and the contents were gently swirled to allow more hydrogenchloride gas to evolve. After most of the gas evolution subsided, theflask was attached to a vacuum aspirator and degassed for 5 min. At theend of the 5 min the flask was attached to a mechanical stirrer and spunslowly (60 rpm) for 16 hr. After 16 hr of spinning, the contents wereplaced on a rotovap in a 100° C. water bath until the gel was dry. Thegel was then poured into a 3 L sintered glass funnel and the gel waswashed successively three times with methanol, three times with DIwater, and three times methanol (400 mL each). The gel was air dried inan open pan overnight and then in an oven at 110° C. for 2 hr. Theweight gain is typically 14-20%.

[0047] 3. Free base poly(allyl amine) (PAA) (M.W. 11,400) (pH=11.5) in a15.4% solution (131 mL), and methanol (69 mL) were mixed in a 500 mLround bottomed flask and swirled until well mixed. The chloropropyl gel(50.00 g), from the previous step, was added to the flask. The contentswere swirled to wet all of the chloropropyl gel and to form a slurry.The contents were degassed using a vacuum aspirator until the foamingstopped. After degassing, the flask was attached to a rotary stirrer,placed in a 50° C. oil bath, and stirred for 3 days. At the end of thestirring process the contents were poured into a 500 mL sintered glassfunnel and washed three times with DI water, once with 4N sulfuric acid,three times with DI water, once with 4N ammonium hydroxide, three timeswith DI water, and two times with methanol (200 mL each). The resultingPAA gel was air dried in an open pan overnight. Typical weight gains arebetween 11-18%.

[0048] 4. 2-picolylchloride hydrochloride (5.27 g) was dissolved inmethanol (9 mL) in a 100 mL round bottomed flask. Triethylamine (11 mL)was added to the flask and the contents were swirled to mix. PAA gel(5.00 g) from the previous step was added to the flask and gentlyswirled to wet the gel and form a slurry. The contents were degassedusing a vacuum aspirator until the evolution of small bubbles stopped.After degassing, the flask was attached to a rotary stirrer, placed in a50° C. oil bath, and stirred for 4 hr. After 4 hr the pH of the solutionwas checked and adjusted to 10.1 with 8 N sodium hydroxide. The slurrywas replaced on the stirrer in the oil bath and stirring continued for atotal of 3 days. At the end of the stirring process the contents werepoured into a 100 mL sintered glass funnel and washed three times withmethanol, three times with DI water, once with conc. sulfuric acid,three times with DI water, and two times with methanol (200 mL each).The resulting D2P-PAA gel was air dried in an open pan overnight.Typical weight gains are between 10-20%.

EXAMPLE 4

[0049] Preparation of silica polyvinylamine/2-pyridine carboxaldehyde(2DPI-PVA).

[0050] In a 3-neck round bottom flask 10 g of PVA gel from step 4 ofExample 1 was mixed with 40 mnL of methanol. The contents were swirleduntil all of the gel was wetted and a slurry was formed. The resultingslurry was degassed for 2 min under vacuum aspiration (until the releaseof small bubbles ceased). The round bottom flask was then fitted to areflux condenser, a glass rod stirred fitted with TEFLON paddle and anitrogen source. The headspace of the flask was purged with nitrogen gasand nitrogen was passed through the reaction vessel throughout thereaction. The heating mantle and condenser cooling water were startedand the temperature of the reactants brought up to the refluxtemperature. 4.3 mL of pyridine carboxaldehyde was added to the contentsof the flask and the reaction carried out at reflux for 2 hours. Aftercooling the resultant slurry was drained by vacuum filtration using afritted glass funnel. Using the same vacuum filtration set-up the gelwas rinsed 3 times with 40 mL of methanol; 3 times with 40 mL of DIwater, 1 time with 40 mL of 4 N sulfuric acid, three times with 40 mL ofDI water, and 2 times with 40 mL of methanol. The resulting buff coloredgel (2PCI-PVA) was then air dried overnight. Typical weight gains 4 werebetween 9 and 12%.

EXAMPLE 5

[0051] Separation of copper (II) from iron (III).

[0052] Gel (2.25 g) as prepared in Example 1 was packed into a plasticcolumn (1.1 centimeter (cm) (diameter) ×4 cm (length)). A challengesolution of 3.93 g of copper sulfate and 14.52 g of ferric chloridedissolved in 1 L of deionized water was pumped through the column at aflow rate of 2 column volumes/min. The challenge solution (70 mL) waspumped through the column followed by DI water (30 mL) and theflowthrough (100 mL) was collected for analysis. Sequestered metal waseluted from the column by pumping concentrated sulfuric acid (5 mL)through the column at a flow rate of 2 column volumes/min followed by DIwater (15 mL) and the eluant (20 mL) was collected for analysis.

[0053] Iron (III) flows through the column while copper (II) is capturedby the column and released into the eluant. FIG. 1 shows the flowthroughcontains the bulk of the iron (III) while FIG. 2 shows most of thecopper appears in the eluant. Typical separation factors are 400-1,100depending upon conditions. The separation factor was derived from thefollowing equation D_(cu)/D_(Fe) where D_(cu)=Cu adsorbed/Cu remainingin solution and D_(Fe)=Fe adsorbed/Fe remaining in solution.

[0054] The simulated mine leachate solution contained approximately 1000parts per million (ppm) Cu⁺⁺ and approximately 3000 ppm Fe⁺⁻⁺. Becausethe column was rinsed with deionized water which was added to theflowthrough prior to analysis, the maximum concentration of ions in theflowthrough was approximately 2100 ppm Fe⁺⁺⁺ and approximately 700 ppmCu⁺⁺.

EXAMPLE 6

[0055] Separation of copper (II) from iron (III) at low concentrations.

[0056] The subject matrix-polyamine based material was compared to acommercially available resin (Dowex XFS-43084) and is more effective atlow copper ion concentrations. The gel of Example 1 having a particlesize of 90-150 μm (90-150 μm D2P-PVA), gel made using the method ofExample 1 and having a particle size of 250-500 μm (250-500 μm D2P-PVA)and XFS 43084 (XFS) a Dowex resin made expressly for the selectiveextraction of copper (II) were compared in batch tests. Bulk XFScontains a large range of particle sizes with the bulk being above 500μm. For the purpose of uniformity the bulk resin was mechanically sievedand the fraction of particles between 250 μm and 500 μm were extracted.The XFS was weighed out for these experiments in the moist dry state inwhich it was received. The subject extraction material was also weighedin the air-dried state. 250-500 μm XFS, 90-105 μm subject gel and250-500 μm subject gel (0.2000 g (±0.0002 g)) were weighed out intoglass screw top vials. 20 mL of a solution containing variousconcentrations of iron (III) only, copper (II) only, and of iron (III)copper (II) mix pH adjusted to 2.0 were added using a volumetricpipette. Table 1 contains the metal ion concentrations in the testsolutions. TABLE 1 Cu in Cu:Fe Mix Fe in Cu:Fe Mix Cu Only Fe Only 0.05M 0.15 M 0.20 M 0.20 M 0.025 M 0.075 M 0.10 M 0.10 M 0.013 M 0.038 M0.050 M 0.050 M 0.0063 M 0.019 M 0.025 M 0.025 M 0.0031 M 0.0094 M 0.013M 0.013 M 0.0016 M 0.0047 M 0.0063 M 0.0063 M 0.00078 M 0.0023 M 0.0031M 0.0031 M

[0057] The vials were placed on a shaker for 24 hr to ensure constantagitation. At that time an aliquot of the metal ion solution was removedfor analysis and preserved with trace metal grade nitric acid. This testwas carried out in triplicate to ensure reliability of the data. Thecollected samples were then diluted to bring the metal concentrationsinto a range which could be analyzed by FAA spectroscopy. After standing24 hr at an elevated pH (2.0) the high iron (III) concentrationsolutions began to form iron (III) precipitates. Negative values appearbecause, at the higher iron (III) concentrations, more iron (III)precipitated out from the control solutions than from the samplescontaining the extraction materials.

[0058]FIG. 3 shows that XFS is efficient at high copper concentrationsbut its effectiveness drops off as the copper concentration decreases.The matrix-based polyamine material of the subject invention howevereffectively removes copper from mixed metal solutions at both high andlow concentrations.

EXAMPLE 7

[0059] Separation of copper (II) from Fe (III) at low pHs.

[0060] 0.2000 g (±0.0002 g) quantities of the extraction material ofExample 1 having a particle size of 90-150 μm (90-150 μm D2P-PVA),extraction material made by the method of Example 1 and having aparticle size of 250-500 μm (250-500 μm D2P-PVA) and XFS resin (Dowex)(XFS) were placed in glass screw top vials. 20 mL aliquots of a 0.0031 MCu⁺⁺ and 0.00934 M Fe⁺⁺⁺ solution were added to the vials using avolumetric pipette. The pHs of the solutions were adjusted to 0.0, 0.5,1.0, 1.5, 2.0 and 2.5 using concentrated sulfuric acid or 8N sodiumhydroxide prior to being placed into the vials. The vials were placed ona shaker to ensure constant agitation. An aliquot of the metal ionsolution was removed for analysis and preserved with trace metal gradenitric acid after 24 hr. Samples were run in triplicate to ensurereliability of the data. Collected samples were diluted to bring themetal concentration into a range which could be analyzed by FAAspectroscopy. pH 2.5 samples was discounted because after 4 hr the iron(III) had significantly precipitated from solution. FIG. 4 shows that atlow pH the extraction material of the subject invention is effective inseparating Cu⁺⁺ from Fe⁺⁺⁺ and at pH 0.5 the 90-150 μm gel is superiorto the Dowex resin. This is important not only in mining process butalso in industry where waste streams can be very acidic. If valuablemetals such as copper can be extracted before the pH is adjusted theywill not have to be recovered from the heavy metal sludge which can formon pH adjustment making recovery easier.

EXAMPLE 8

[0061] Useable gel lifetime.

[0062] Longevity tests were carried out in the following manner. 5 cubiccentimeter column were loaded with the gel prepared in Example 1(D2P-PVA) or Dowex XFS resin (XFS). 100 mL of DI water was pumpedthrough each column to wet the material. Then, 70 mnL of a 1000 ppmCu⁺⁺: 3000 ppm Fe⁺⁺⁺, from copper sulfate and ferric chloride, solutionwas pumped through the column at a flow rate of 2 column volumes/min andthe flowthrough was collected. 30 mL of DI water was then pumped througheach column to rinse the column. The rinse water was collected along theflowthrough. The collected solutions were preserved with trace metalgrade nitric acid and diluted to enable FAA spectroscopic analysis forCu⁺⁺ and Fe⁺⁺⁺. The columns were then stripped of metal by pumping 4 mnLof sulfuric acid through the column. The XFS column was stripped with 8NH₂SO₄ while the D2P-PVA column was stripped with concentrated acid. Thestrip solution as well as 16 mL of DI water were collected and laterdiluted for analysis for Fe⁺⁺ and Cu⁺⁺⁺ by FAA spectroscopy. The columnswere then rinsed with 100 mL of DI water. The rinse water was discarded.

[0063] When not collecting capacity samples, the columns were attachedto a six-way manifold equipped with solenoid valves wired to a computercontaining software to carry out the following cycle. The pump wasadjusted to produce a flow rate of 10 column volumes/min. The challengesolution was pumped through for 6 seconds (sec) followed by DI water for10 sec. Concentrated sulfuric acid was pumped through the columns for 5sec. A 36 sec rinse with DI water completed the cycle.

[0064] The metal ion capacity was checked after 25, 75, 150, 300, 450,700, 1000, and 1500 cycles. The absorbence data from the FAA wasconverted to millimoles of metal ion per g of extractive material andplotted. FIG. 5 shows that at 1500 cycles both materials seem to haveretained their capacity for copper (II) and rejection for iron (III). Itis also clear from FIG. 5 that at a flow rate of 2 column volumes/min90-105 micron D2P-PVA has a higher copper (II) capacity than XFS.D2P-PVA also has a greater separation power demonstrated by the distancebetween the copper (II) and iron (III) lines of the graph.

EXAMPLE 9

[0065] Flow capacity.

[0066] Flow capacity tests indicate how a material may perform in aprocess setting. Flow capacity tests were conducted with the procedureoutlined in paragraph one of Example 7. The results of these test forfive materials are presented in Table 2. TABLE 2 Cu⁺⁺ Capacity Fe⁺⁺⁺Capacity Separation Material (mmol/g) (mmol/g) Factor  90-105 μM D2P-PVA0.369 0.006 1046.8 250-500 μm XFS 0.187 0.021 60.0  90-105 μm D2P-PEI0.182 0.008 130  90-105 μm 2PCI-PVA 0.253 0.006 429.3 250-500 D2P-PVA0.109 0.015 32.9

[0067] The separation factor was defined as Separation Factor=q_(e)^(Cu)/C_(e) ^(Cu)/q_(e) ^(Fe)/C_(e) ^(Fe) where q_(e) ^(Cu), q_(C) ^(Fe)are the amount of copper and iron adsorbed onto the extractant atequilibrium respectively and C_(e) ^(Cu), C_(e) ^(Fe) are the amount ofcopper and iron in solution at equilibrium respectively.

[0068] It is understood that the foregoing examples are merelyillustrative of the present invention. Certain modifications of thecompositions and/or methods employed may be made and still achieve theobjectives of the invention. Such modification are contemplated aswithin the scope of the claimed invention.

1. An extraction material for separating at least one transition metalion species from iron (III) in a solution, said extraction materialcomprising a matrix-polyamine base and a pyridine functional group, saidmatrix-polyamine base comprising the reaction product of a polyaminewith a short chain hydrocarbylsilyl formed from first silanizing amatrix surface by hydrating said surface and reacting said hydratedsurface with a short chain trifunctional silane having (a) hydrocarbonsubstituents containing 1-6 carbon atoms, (b) trifunctional leavinggroups providing sites for covalently bonding said hydrocarbylsilyl tosaid matrix surface through Si—O bonds, and (c) terminal leaving groupsproviding sites for covalently bonding said polyamine to saidhydrocarbylsilyl through N-hydrocarbyl bonds; and secondly reacting saidpolyamine with said hydrocarbylsilyl formed from the silanization ofsaid hydrated surface so as to form an aminohydrocarbyl polymercovalently bound to said matrix surface, said aminohydrocarbyl polymerhaving non-crosslinked amino groups multisite bound to saidhydrocarbylsilyl.
 2. The extraction material of claim 1, wherein saidsilane has trifunctional substituents selected from the group consistingof trichloro, trimethoxy and triethoxy substituents.
 3. The extractionmaterial of claim 1, wherein said silane has terminal leaving groupsubstituents selected from the group consisting of halogens, tosylate,mesylate, brosylate and triflate.
 4. The extraction material of claim 1,wherein said hydrocarbon substituents are short chain aliphatichydrocarbons having 1-6 carbon atoms.
 5. The extraction material ofclaim 1, wherein said silane has trifunctional substituents selectedfrom the group consisting of trichloro, trimethoxy and triethoxysubstituents; said silane has terminal leaving group substituentsselected from the group consisting of halogens, tosylate, mesylate,brosylate and triflate; and said hydrocarbon substituents are shortchain aliphatic hydrocarbons having 1-6 carbon atoms.
 6. The extractionmaterial of claim 5, wherein said silane is bromopropyltrichloro silane.7. The extraction material of claim 5, wherein said silane ischlorpropyltrichloro silane.
 8. The extraction material of claim 1,wherein polyamine is polyvinylamine.
 9. The extraction material of claim1, wherein said polyamine is polyethyleneimine.
 10. The extractionmaterial of claim 1, wherein said polyamine is polyallylamine.
 11. Theextraction material of claim 1, wherein said pyridine functional groupis a pyridine alkylamine with an alkyl chain of about 1-4 carbons. 12.The extraction material of claim 1, wherein said pyridine functionalgroup is a pyridine alkyl aldehyde with an alkyl chain about 1-4carbons.
 13. The extraction material of claim 1, wherein said pyridinefunctional group is 2-picolylamine.
 14. The extraction material of claim1, wherein said pyridine functional group is 2-pyridine carboximene. 15.The extraction material of claim 8, wherein said pyridine functionalgroup is 2-picolylamine.
 16. The extraction material of claim 8, whereinsaid pyridine functional group is 2-pyridine carboxmine.
 17. Theextraction material of claim 9, wherein said pyridine functional groupis 2-picolyamine.
 18. The extraction material of claim 9, wherein saidpyridine functional group is 2-pyridine carboximiine.
 19. The extractionmaterial of claim 10, wherein said pyridine functional group is2-picolyamine.
 20. The extraction material of claim 10, wherein saidpyridine functional group is 2-pyridine carboximine.
 21. The extractionmaterial of claim 1, wherein said silane is bromopropyltrichloro silane,said polyamine is polyvinylamine and said pyridine functional group is2-picolyamine.
 22. The extraction material of claim 1, wherein saidsilane is chloropropyltrichloro silane, said polyamine is polyvinylamineand said pyridine functional group is 2-picolyamine.
 23. The extractionmaterial of claim 1, wherein said silane is bromopropyltrichloro silane,said polyamine is polyvinylamine and said pyridine functional group is2-pyridine carboxmine.
 24. The extraction material of claim 1, whereinsaid silane is chloropropyltrichloro silane, said polyamine ispolyvinylamine and said pyridine functional group is 2-pyridinecarboximine.
 25. The extraction material of claim 1, wherein said silaneis bromopropyltrichloro silane, said polyamine is polyethyleneimine andsaid pyridine functional group is 2-picolyamine.
 26. The extractionmaterial of claim 1, wherein said silane is chloropropyltrichlorosilane, said polyamine is polyethyleneimine and said pyridine functionalgroup is 2-picolyamine.
 27. The extraction material of claim 1, whereinsaid silane is bromopropyltrichloro silane, said polyamine ispolyethyleneimine and said pyridine functional group is 2-pyridinecarboximine.
 29. The extraction material of claim 1, wherein said silaneis bromopropyltrichloro silane, said polyamine is polyallylamine andsaid pyridine functional group is 2-picolyamine.
 30. The extractionmaterial of claim 1, wherein said silane is chloropropyltrichlorosilane, said polyamine is polyallylamine and said pyridine functionalgroup is 2-picolyamine.
 31. The extraction material of claim 1, whereinsaid silane is bromopropyltrichloro silane, said polyamine ispolyallylamine and said pyridine functional group is 2-pyridinecarboximine.
 32. The extraction material of claim 1, wherein said silaneis chloropropyltrichloro silane, said polyamine is polyallylamine andsaid pyridine functional group is 2-pyridine carboximine.
 33. Theextraction material of claim 1, wherein said at least one transitionmetal ion species is copper (II).
 34. A method of making an extractionmaterial for separating at least one transition metal ion species fromiron (III) ions in a solution comprising the steps of: a) providing amatrix having a surface that is silanizable; b) hydrating said surfaceof said matrix with a monolayer of water; c) silanizing said hydratedsurface of said matrix with a silane having short chain hydrocarbylsubstituents containing 1-6 carbon atoms and terminal leaving groups soas to hydrocarbylate said matrix surface, said terminal leaving groupsproviding sites for covalently bonding a polyamine to thehydrocarbylsilyil through N--hydrocarbyl bonds; d) reacting saidpolyamine with said hydrocarbylated matrix surface after silanization iscomplete to form an aminohydrocarbyl polymer covalently bound to thehydrocarbylated extraction material surface with said aminohydrocarbylpolymer having non-crosslinked amino groups multisite bound to saidhydrocarbylsilyl; and e) reacting a pyridine functional group with saidaminohydrocarbyl polymer.
 35. The method of claim 34, wherein saidsilane has trifunctional substituents selected from the group consistingof trichloro, trimethoxy and triethoxy substituents.
 36. The method ofclaim 34, wherein said silane has terminal leaving group substituentsselected from the group consisting of halogens, tosylate, mesylate,brosylate and triflate.
 37. The method of claim 34, wherein saidhydrocarbon substituents are short chain aliphatic hydrocarbons having1-6 carbon atoms.
 38. The method of claim 3 4, wherein said silane hastrifunctional substituents selected from the group consisting oftrichloro, trimethoxy and triethoxy substituents; said silane hasterminal leaving group substituents selected from the group consistingof halogens, tosylate, mesylate, brosylate and triflate; and saidhydrocarbon substituents are short chain aliphatic hydrocarbons having1-6 carbon atoms.
 39. The method of claim 34, wherein said silane isbromopropyltrichioro silane.
 40. The method of claim 34, wherein saidsilane is chloropropyltrichloro silane.
 41. The method of claim 34,wherein said polyamine is polyvinylamine.
 42. The method of claim 34,wherein said polyamine is polyethyleneimine.
 43. The method of claim 34,wherein said polyamine is polyallylamine.
 44. The method of claim 3 4,wherein said pyridine functional group is a pyridine ring, with an alklchain of about 1-4 carbons with a terminal halogen selected from thegroup consisting of tosylate, mesylate, brosylate and tritlate.
 45. Themethod of claim 34, wherein said pyridine functional group is a pyridineling with an alkyl chain of about 1-4 carbons with a terminal aidehyde.46. The method of claim 34, wherein said pyridine functional group ispicolyichloride hydrochloride.
 47. The method of claim 34, wherein saidpyridine functional group is pyridine 2-carboxaldehyde.
 48. The methodof claim 41, wherein said pyridine functional group is picolylchloridehydrochloride.
 49. The method of claim 41, wherein said pyridinefunctional group is pyridine 2-carboxaldehyde.
 50. The method of claim42, wherein said pyridine functional group is picolylchioridehydrochloride.
 51. The method of claim 42, wherein said pyridinefunctional group is pyridine 2-carboximine.
 52. The method of claim 43,wherein said pyridine functional group is picolychloride hydrochloride.53. The method of claim 43, wherein said pyridine functional group ispyridine 2-carboxaldehyde.
 54. The method of claim 34, wherein said atleast one transition metal ion species is copper (II).
 55. A process forseparating at least one transition metal ion species from iron (III)ions in a solution comprising at least one transition metal ion species,iron (III) ions and chloride ions said process comprising the steps of:a) applying said solution to an extraction material comprising amatrix-polyamine base and a pyridine functional group, saidmatrix-polyamine base comprising the reaction product of a polyaminewith a short chain hydrocarbylsilyl formed from first silanizing amatrix surface by hydrating said surface and reacting said hydratedsurface with a short chain trifunctional silane having (a) hydrocarbonsubstituents containing 1-6 carbon atoms, (b) trifunctional leavinggroups providing sites for covalently bonding said hydrocarbylsilyl tothe extraction material surface through Si—O bonds, and (c) terminalleaving groups providing sites for covalently bonding said polyamine tosaid hydrocarbylsilyl through-hydrocarbyl bonds; and secondly reactingsaid polyamine with said hydrocarbylsilyl formed from the silanizationof said hydrated surface so as to form an aminohydrocarbyl polymercovalently bound to said matrix surface, said aminohydrocarbyl polymerhaving non-crosslinked amine groups multisite bound to saidhydrocarbylsilyl, wherein said amino/imino pyridine functional groupbinds and selectively extracts said transition metal ions from saidsolution; b) purging said transition metal ions bound to said extractionmaterial of cholide ions; and c) stripping said bound transition metalions from said extraction material.
 56. The process of claim 55, whereinsaid silane has trifunctional substituents selected from the groupconsisting of trichloro, trimethoxy and triethoxy substituents.
 57. Theprocess of claim 55, wherein said silane has terminal leaving groupsubstituents selected from the group consisting of halogens, tosylate,mesylate, brosylate and triflate.
 58. The process of claim 55, whereinsaid hydrocarbon substituents are short chain aliphatic hydrocarbonshaving 1-6 carbon atoms.
 59. The extraction material of claim 55,wherein said silane has trifunctional substituents selected from thegroup consisting of trichloro, trimethoxy and triethoxy substituents;said silane has terminal leaving group substituents selected from thegroup consisting of halogens, tosylate, mesylate, brosylate andtrifiate; and said hydrocarbon substituents are short chain aliphatichydrocarbons having 1-6 carbon atoms.
 60. The process of claim 55,wherein said silane is bromopropyltrichloro silane.
 61. The process ofclaim 55, wherein said silane is chloropropyltricholoro silane.
 62. Theprocess of claim 55, wherein said polyamine is polyvinylamine.
 63. Theprocess of claim 55, wherein said polyamine is polyethyleneimine. 64.The process of claim 55, wherein said polyamine is polyallylamine. 65.The process of claim 55, wherein said pyridine functional group is apyridine alkylamine with an alkyl chain of about 1-4 carbons.
 66. Theprocess of claim 55, wherein said pyridine functional group is apyridine alkyl aldehyde with an alkyl chain about 1-4 carbons.
 67. Theprocess of claim 55, wherein said pyridine functional group is2-picolylamine.
 68. The process of claim 55, wherein said pyridinefunctional group is 2-pyridine carboximene.
 69. The process of claim 62,wherein said pyridine functional group is 2-picolylamine.
 70. Theprocess of claim 62, wherein said pyridine functional group is2-pyridine carboxmine.
 71. The process of claim 63, wherein saidpyridine functional group is 2-picolylamine.
 72. The process of claim63, wherein said pyridine functional group is 2-pyridine carboximine.73. The process of claim 64, wherein said pyridine functional group is2-picolylamine.
 74. The process of claim 64, wherein said pyridinefunctional group is 2-pyridine carboximine.
 75. The process of claim 55,wherein said chloride ions are purged with a solution selected from thegroup consisting of saturated sodium sulfate and dilute sulfuric acid.76. The process of claim 55, wherein said copper (II) ions are strippedfrom said extraction material with sulfuric acid.
 77. The process ofclaim 55, wherein said extraction material is in a column.
 78. Theprocess of claim 55, wherein said at least one transition metal ionspecies is copper (II).